Preparation of new derivatives of aromatic amines



Patented June 5, 1945 OFFICE PREPARATION OF NEW DERIVATIVES OF AROMATIC AMINES,

Gastao EtzeL-Newark, Del., asslmor to E. I. du

Pont

de Nemonrs & Company, Wilmin non,

Del., a corporation of Delaware N Drawing. Application May 27, 1942,

- Serial No. 444,685

. Claims. (01. 260576) This invention relates to processes for the preparation of new derivatives of aromatic amines. More particularly it relates to the condensation of primary aromatic amines with a terpene hydrocarbon in the presence of a surface active aluminum or magnesium hydr'osilicate. The invention also relates to novel aromatic amine derivatives obtainable by the processes just described.

This invention has for an object the provision of a new derivative of aromatic amines. A further object is to prepare such derivative by a simple process. parent from the hereinafter described invention.

The above objects are accomplished by, heating a primary aromatic amine with a terpene hydrocarbon-in the presence of a surface active catalyst comprising an aluminum or magnesium hydrosilicate.

The terpene hydrocarbon and an excess of the primary aromatic amine are heated in admixture at normal or elevated pressure with a material amount by weight of a surface active aluminum or magnesium hydrosilicate or a mixture of such hydrosilicates. A temperature of at 1 takes place quite readily. However, even at the low reaction temperatures some nuclear substituted or primary terpenyl aromatic amines are Still other objects will be ap-' is reacted with a molar excess of an aromatic.

primary amine such as aniline at a temperature of from 100 to 300 C. for a period of 8 to 50 hours. i

The .invention will be further illustrated but is not intended to be limited by the following examples. i 4

Example I A mixture of 500 parts by weight or camphene and 513 parts of aniline was heated to 140 C.

under atmospheric pressure and 100 parts or fullers earth was added, in portions, during a period of 90 minutes. The mixture was heated at 140 C. forv 10 hours, cooled and filtered; The

least 50 C. is maintained until an appreciable was heated in an autoclave at 250 C. for 40 hours.

formed. Some isomerization. of the terpene nuv cleus may take place; for example, the final configuration from camphene may be of a bornyl structure.

After completiOn of the reaction the catalyst can be removed by filtration and the reaction product fractionally distilled to separate the condensation product from the unreacted'amine.

The aromatic amine and terpene hydrocarbon, if liquids, can be admixed by simple stirring. If normally solid they can be liquefied separately or together by heatin and the surface active catalyst added. However, inert organic solvents such product was fractionaily distilled under reduced pressure. The fraction boiling at 165 C. at 5 mm. pressure consisted of a mixture of primary and secondaryterpenyl anilines.

Example I! A mixture of 1500 parts by weight of camphene.

1438 parts of aniline and 225 parts of fullers earth was heated in an autoclave at 200 C. for 10 hours. The reaction product was cooled, filtered and fractionally distilled. The fraction boiling at 161-163 C. at 5 mm. consisted of a mixtureot terpenyl anilines ofwhich 13.8% was primary amine.

' a Example III A mixtureof 150 parts by weight of camphene, 115 parts of aniline and 25 parts of fullers earth The crude mixture was cooled, filtered and fractionally distilled. The portion boiling at 219- 226 C. under 40 pressure consisted of a mixture of primary and secondary mono-terpenyl anilines of which 80% was primary amine.

' Example IV Y porous aluminum hydrosilicate having the approximate composition S10: 48.9%; moisture 12.6%; FeaOa 1.2%; A1203 36.4%, and total alkali as oxide, 0.5%, was heated in an autoclave at 250 C. for 12 hours. The product was recovered pressure.

as in the preceding examples and consisted of a mixture of primary andsecondary monoterpenyl anilines.

' Example V A mixture of 150 parts by weight of camphene,

-- 145 parts of orthotoluidine and 30 parts of Iullers earth was heated in an autoclave at 250 C. for 40 hours. The mixture of monoterpenyl amines was recovered as in the preceding example and had a boiling range of 200-240" C. at 40-50 mm.

pressure. A fraction of primary monoterpenyl amine was recovered at 235-240 C. at 50 mm Example VI A mixture of 100 parts by weight or pinene, 100 parts of aniline and 22 parts or i'ullers earth was heated in an autoclave at 200 for '10 hours. The crude product was cooled, filtered and Iractionated under reduced pressure. The portionboiling at 178-185 C. under'10-12 mm. pressure consisted oi monoterpenyl anilines of which about 65% was primary amine.

Example VI] A mixture '01 10 parts by weight of dipentene. 10 parts of aniline and 2 parts of iullers earth was heated in an autoclave at 200 C. for 10,

hours. -'The product was recovered as in the preceding examples and had a boiling range of 160-165 C. at 5 mm. and 70%- of the monoterpenyl anilines was primary amine.

Example W1] -A mixture r '150 parts by weight a mixedterpene hydrocarbons obtainable as by-products in the isomerization of inene to camphene as described in United States Patent 2,129,323, 564 parts or aniline and 150 parts or iullers earth was heated in an autoclave at 200 C. for hours. The product, recovered as in the preceding examples, consisted of monoterpenyl anilines boiling at 190-197 C. under 5-10 mm. pressure.

The invention is not limited to the condensaamines include toluidineaaand p-naphthylamine, xylidenes, uand p-amino-anthraquinone and diphenylamines.

Various other active aluminum and magnesium hydrosilicates can be used in place of the fullers earth of the above examples. Florida earth and other bleaching earths which are activated by treatment with acids such as in-'; 'fusorial earth, tonsil, bentonite, etc., can be substituted in like manner. In U. S. P. 1,936,587 are described such earths and others sold under various trade names which can be utilized in accordance with the teachings hereof.

The catalysts just described can be used over a fairly wide range of amounts. In general, at least 3% by weight of the amine and terpene is required and up to 30% may be used. A prebe limited to the specific embodiments hereof,

except as defined in the appended claims.

I claim:

1. The process which comprises reacting in admixture an aromatic primary amine and a terpene hydrocarbon in the presence of a surtion of the specific terpene hydrocarbons mentioned in the above examples. 0n the contrary, any unsaturated terpene hydrocarbons can be used in like manner. Cyclic terpenes, however, constitute preferred reactants. Among the use- Iul additional terpenes which can be substituted for the terpenes in the above examples are menthene, limonene, terpinolene, terpinene, alloocimene, dihydrcmyrcene and alpha thujene.

' Mixtures of two or more of the herein disclosed terpenes and especially the mixtures of terpene hydrocarbons formed as by-products in the isomeriz'a'tion or pinene to camphene can be reacted with one or more aromatic amines.

In place of aniline as the aromatic amine described in the above examples can be substituted other aromatic primary amines. including mono-, di and polyamines. Suitable other race active hydrosilicate taken from the class consisting of aluminum and magnesium hydrosilicates.

2. The process which comprises heating in admixture an 'aromatic primary amine and aterpene hydrocarbon to a temperature from to 300 C. for a period of at least 5 hours in the 'presence of a, surface active hydrosilicate taken from the class consisting of aluminum and magnesium hydrosilicates.

3. The process which comprises heating in admixture amolar excess of an aromatic primary amine and a terpene hydrocarbon to a temperature from 50 C. to 300 C. for a period one to 40 hours in the presence of from 5% to 20% by weight, based on the combined weight of said primary amine and terpene hydrocarbon, of a surface active hydrosilicatetaken from the class consisting of aluminum and magnesium hydrosilicates.

4. A process as set forth in claim 3 wherein said hydrosilicate is fullers earth.

5. A process as set forth in claim 3 wherein said terpene is a cyclic terpene.

- GASTA O E'IZEL. 

